CN109755638A - The preparation method and applications of composite electrolyte membrane, composite electrolyte membrane - Google Patents
The preparation method and applications of composite electrolyte membrane, composite electrolyte membrane Download PDFInfo
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Abstract
The present invention provides the preparation method and applications of a kind of composite electrolyte membrane, composite electrolyte membrane.Composite electrolyte membrane includes following each component: the thio lithium fast-ionic conductor of the nanoscale of 10wt.%~60wt.%；The lithium salts of 10wt.%~40wt.%；Polyethylene glycol oxide；And poly- propene carbonate.Wherein, the mass ratio of polyethylene glycol oxide and poly- propene carbonate is 1: 5~50: 1.
Description
Technical field
The present invention relates to technical field of lithium ion, the system of especially a kind of composite electrolyte membrane, composite electrolyte membrane
Preparation Method and its application.
Background technique
The electrolyte of lithium ion battery generallys use organic electrolyte at present, overcharges, the abnormal conditions such as internal short-circuit
It is easy to cause battery-heating, causes electrolyte inflatable, spontaneous combustion even to explode, there are severe compromises.Using solid electrolyte
Solid state lithium battery is constructed, the security risk caused by leakage can be thoroughly avoided.In addition, solid state lithium battery also has self-discharge rate
The low, advantages such as operation temperature area is wide, electrochemical stability window is wide.
Solid electrolyte can be divided into inorganic solid electrolyte and solid polyelectrolyte.Inorganic solid electrolyte room temperature lithium
Ionic conductivity is high, and thermal stability is high, electrochemical window mouth width, but brittleness is larger, flexibility is poor, and bad, interface is contacted with electrode
Resistance is high, and preparation cost is higher.Solid polyelectrolyte has better flexibility and viscoplasticity, can compensate for charge and discharge
The volume change of electric process electrode material, it is high with the stickiness of electrode, and easily form a film, machine-shaping is easy, and cost is relatively low, but
Ionic conductivity is relatively low, and generally less than 10-5S/cm。
For improve inorganic solid electrolyte and electrode interfacial contact situation, in the prior art by inorganic solid electrolyte with
Polymer dielectric is compound, but ineffective.Moreover, other than ionic conductivity and interfacial contact problem, electrolyte and electricity
The chemical compatibility of pole material is also the key factor for limiting solid state lithium battery performance.
Summary of the invention
The advantages of inorganic solid electrolyte and solid polyelectrolyte can be taken into account the object of the present invention is to provide one kind,
It can improve again and the composite electrolyte membrane of the chemical compatibility of electrode material, composite electrolyte membrane preparation method and applications.
In order to solve the above technical problem, the present invention provides a kind of composite electrolyte membrane, including following each component:
The thio lithium fast-ionic conductor of the nanoscale of 10wt.%~60wt.%；The lithium salts of 10wt.%~40wt.%；Polyethylene glycol oxide；And
Poly- propene carbonate.Wherein, the mass ratio of polyethylene glycol oxide and poly- propene carbonate is 1: 5~50: 1.
More preferably, the thio lithium fast-ionic conductor 20wt.%~40wt.% of nanoscale, lithium salts 20wt.%~
The mass ratio of 30wt.%, polyethylene glycol oxide and poly- propene carbonate is 1: 3~10: 1.
Optionally, the thio lithium fast-ionic conductor of nanoscale includes Li4-xSi1-xPxS4-yAyOne or more of, A is in formula
F, Cl, Br or I, 0≤y≤0.5；The particle size of the thio lithium fast-ionic conductor of nanoscale is 10nm~100nm.
Optionally, lithium salts includes lithium perchlorate, lithium hexafluoro phosphate, LiBF4, dioxalic acid lithium borate, trifluoromethyl sulphur
One or more of sour lithium, bis- (trifluoromethane sulfonic acid) imine lithiums and three (trifluoromethane sulfonic acid) lithium methides.
Optionally, 100 μm~400 μm of the thickness of composite electrolyte membrane, the ionic conductivity of composite electrolyte membrane is 2 ×
10-5S/cm~2 × 10-4S/cm, composite steps carry out at 25 DEG C~60 DEG C
In the second aspect of the invention, the present invention also provides a kind of preparation methods for preparing composite electrolyte membrane, including
Prepare the thio lithium fast-ionic conductor step of meter level and composite steps.Prepare the thio lithium fast-ionic conductor step of meter level: by Li2S、
AS2、P2S5And halogen dispersion is in organic solvent, obtains precursor powder after evaporating solvent, receiving for halogen doping is obtained after calcining
The thio lithium fast-ionic conductor of meter level, in formula, AS2For SiS2、GeS2And SnS2In any one；Composite steps: by polyoxyethylene
The thio lithium fast-ionic conductor of nanoscale and lithium salts of halogen doping is added in alkene, poly- propene carbonate and organic solvent Hybrid Heating,
It is uniformly dispersed, pours into molding die, obtain composite electrolyte membrane after evaporation at constant temperature solvent.
It is according to the invention this aspect, organic solvent be anhydrous acetonitrile, dimethyl sulfoxide, n,N-Dimethylformamide and
One or more of N-Methyl pyrrolidone.
This aspect according to the invention, the temperature of calcining are 300 DEG C~600 DEG C, the heating rate of calcining is 0.1 DEG C/
Min~10 DEG C/min, calcination time 4h~2h.
In the third aspect of the invention, the present invention also provides a kind of application of composite electrolyte membrane, composite electrolyte membranes
For in lithium battery.
This aspect according to the invention, is dissolved in organic solvent for polyethylene glycol oxide and lithium salts, is coated to composite electrolyte
On film, vacuum constant temperature is dry after solvent evaporation, obtains the composite electrolyte membrane of polyoxyethylene ene coatings protection.
It is according to the invention this aspect, polyoxyethylene ene coatings with a thickness of 5 μm~50 μm, preferably 10 μm~30 μ
M, the temperature of solvent evaporation are 25 DEG C~60 DEG C, and the dry temperature of vacuum constant temperature is 40 DEG C~80 DEG C, vacuum constant temperature it is dry when
Between 3h~48h.
To sum up, composite electrolyte membrane of the present invention had both improved that interfacial contact between electrolyte and electrode is bad, Intergranular impedance
Big problem, and higher ionic conductivity is maintained, while it is poor to solve chemical compatibility between electrolyte and negative electrode material
Problem, have broad application prospects in solid state lithium battery field.
Detailed description of the invention
Fig. 1 is X-ray diffraction (XRD) figure for the thio lithium fast-ionic conductor of nanoscale that the embodiment one in the present invention provides
Spectrum；
Fig. 2 is the scanning electron microscope map for the thio lithium fast-ionic conductor of nanoscale that the embodiment one in the present invention provides；
Fig. 3 is the scanning electron microscope map for the composite electrolyte membrane that the embodiment one in the present invention provides；
Fig. 4 is the AC impedance curve for the composite electrolyte membrane that the embodiment one in the present invention provides；
Fig. 5 is the constant current charge-discharge loop test curve for the composite electrolyte membrane that the embodiment one in the present invention provides；
Fig. 6 is the capacitor cycle performance figure for the composite electrolyte membrane that the embodiment one in the present invention provides.
Specific embodiment
With reference to the accompanying drawings and examples, specific embodiments of the present invention will be described in further detail.Following instance
For illustrating the present invention, but it is not intended to limit the scope of the invention.
The chemical formula of bis- (trifluoromethane sulfonic acid) imine lithiums in the present invention is LiN (SO2CF3)2, the present invention in three (three
Methyl fluoride sulfonic acid) lithium methide be chemical formula be LiC (SO2CF3)3。
Embodiment one
Thio lithium fast-ionic conductor base composite solid electrolyte film (the abbreviation composite electrolyte of nanoscale that embodiment one provides
Film), by Li9.54Si1.74P1.44S11.7Cl0.3, polyethylene glycol oxide, poly- propene carbonate and bis- (trifluoromethane sulfonic acid) imine lithium groups
At.Composite electrolyte membrane with a thickness of 200 μm, at room temperature ionic conductivity be 2 × 10-4S/cm。
Wherein, Li9.54Si1.74P1.44S11.7Cl0.3The mass ratio accounted in composite electrolyte membrane is 40%.
The mass ratio that poly- propene carbonate accounts in composite electrolyte membrane is 30%.
The mass ratio that polyethylene glycol oxide accounts in composite electrolyte membrane is 10%.
The mass ratio that bis- (trifluoromethane sulfonic acid) imine lithiums account in composite electrolyte membrane is 20%.
Embodiment one also provides a kind of preparation method and applications of composite electrolyte membrane.Compound electric provided in this embodiment
Solution plasma membrane is specific the preparation method is as follows: including receiving to prepare the thio lithium fast-ionic conductor step of meter level, composite steps and polyoxygenated
The preparation of vinyl coating, wherein
It receives and prepares the thio lithium fast-ionic conductor step of meter level:
(1) Li is stoichiometrically weighed2S、SiS2、P2S5And LiCl is added in anhydrous acetonitrile, magnetic agitation for 24 hours, is dispersed
After uniformly, solvent is evaporated while stirring, obtains precursor powder；
(2) gained precursor powder calcines 6h at 400 DEG C, obtains nanoscale Li9.54Si1.74P1.44S11.7Cl0.3。
Composite steps:
(1) polyethylene glycol oxide, poly- propene carbonate and anhydrous acetonitrile are mixed according to the ratio of mass ratio 1: 3: 50,50
Magnetic agitation 2h at DEG C sufficiently dissolves；
(2) Li is weighed by metering ratio9.54Si1.74P1.44S11.7Cl0.3It is added with bis- (trifluoromethane sulfonic acid) imine lithiums above-mentioned
Solution, ultrasonic disperse are uniform；
(3) above-mentioned solution is poured into polytetrafluoro molding die, evaporation at constant temperature solvent, obtains composite electrolyte at 60 DEG C
Film.
The preparation of polyoxyethylene ene coatings:
(1) in mass ratio 4: 1 weigh polyethylene glycol oxide and bis- (trifluoromethane sulfonic acid) imine lithiums addition anhydrous acetonitrile, 50 DEG C
Lower magnetic agitation 2h, dissolution are abundant；
(2) the composite electrolyte film surface for preparing above-mentioned solution coating to step 2, evaporation at constant temperature solvent at 60 DEG C；
(3) composite electrolyte membrane of gained coating protection is dried in vacuo 8h at 50 DEG C, further removes anhydrous acetonitrile, i.e.,
The composite electrolyte membrane of coating protection can be obtained.
Fig. 1 is Li prepared by the present embodiment one9.54Si1.74P1.44S11.7Cl0.3XRD diagram, it is known that, this method preparation master
Product is Li9.54Si1.74P1.44S11.7Cl0.3, there are a small amount of by-product Li3PS4, Li3PS4It also being capable of conducting lithium ions.Fig. 2 is this
Li prepared by embodiment one9.54Si1.74P1.44S11.7Cl0.3SEM figure, Li9.54Si1.74P1.44S11.7Cl0.3Particle size it is equal
It is even, about 30nm~50nm.Fig. 3 is the SEM figure of composite electrolyte membrane prepared by the present embodiment one, from figure as it can be seen that composite electrolyte
Film surface is uniform, has no apparent sulfide bulky grain, illustrates that obviously reuniting does not occur in composite membrane-forming process sulfide, and by
Polymer wrapped avoids directly contacting with electrode material, improves chemical stability.
Composite electrolyte membrane prepared by the present embodiment one is assembled into symmetrical obstruction battery, obstruction electricity is made with stainless steel gasket
Pole, gained ac impedance spectroscopy is as shown in figure 4, the ionic conductivity for calculating gained composite electrolyte membrane is 2 × 10-4S/cm。
The composite electrolyte membrane of coating protection prepared by embodiment one is washed into the disk that diameter is 15mm, as electrolyte
Film assembles solid lithium ion battery.Anode by LiFePO4, superconductive carbon black (Super P),
Li9.54Si1.74P1.44S11.7Cl0.3It being formed with Kynoar (PVDF) in mass ratio 75: 10: 9: 6, cathode is metal lithium sheet,
Battery is assemblied in argon gas glove box and carries out.Constant current charge-discharge loop test is carried out to solid lithium ion battery, 0.1C electric current is close
Under degree, solid state battery initial capacity is 166.5mAh/g, and capacity retention ratio is 90.5% after circulation 30 weeks.
Embodiment two
The thio lithium fast-ionic conductor base composite solid electrolyte film of nanoscale that embodiment two provides, by
Li9.54Si1.74P1.44S11.7I0.3, polyethylene glycol oxide, poly- propene carbonate and lithium perchlorate composition.The thickness of composite electrolyte membrane
It is 150 μm, ionic conductivity is 1 × 10 at room temperature-4S/cm。
Wherein, Li9.54Si1.74P1.44S11.7I0.3The mass ratio accounted in composite electrolyte membrane is 20%.
The mass ratio that poly- propene carbonate accounts in composite electrolyte membrane is 25%.
The mass ratio that polyethylene glycol oxide accounts in composite electrolyte membrane is 25%.
The mass ratio that lithium perchlorate accounts in composite electrolyte membrane is 30%.
Embodiment two also provides a kind of preparation method and applications of composite electrolyte membrane, specific the preparation method is as follows: packet
Include the preparation received and prepare the thio lithium fast-ionic conductor step of meter level, composite steps and polyoxyethylene ene coatings, wherein
It receives and prepares the thio lithium fast-ionic conductor step of meter level:
(1) Li is stoichiometrically weighed2S、SiS2、P2S5It is added in n,N-Dimethylformamide with LiI, magnetic agitation
36h after being uniformly dispersed, evaporates solvent while stirring, obtains precursor powder；
(2) gained precursor powder calcines 3h at 600 DEG C, obtains nanoscale Li9.54Ge1.74P1.44S11.7I0.3。
Composite steps:
(1) ratio of polyethylene glycol oxide, poly- propene carbonate and N,N-dimethylformamide in mass ratio 1: 1: 25 is mixed
It closes, at room temperature magnetic agitation 1h, sufficiently dissolves；
(2) Li is weighed by metering ratio9.54Si1.74P1.44S11.7I0.3Above-mentioned solution, magnetic agitation is added with lithium perchlorate
36h is uniformly dispersed；
(3) above-mentioned solution is poured into polytetrafluoro molding die, evaporation at constant temperature solvent, obtains composite electrolyte at 40 DEG C
Film.
The preparation of polyoxyethylene ene coatings:
(1) in mass ratio 7: 3 polyethylene glycol oxide and lithium perchlorate addition n,N-Dimethylformamide are weighed, room temperature magnetic force stirs
4h is mixed, dissolution is abundant；
(2) the composite electrolyte film surface for preparing above-mentioned solution coating to step 2, evaporation at constant temperature solvent at 40 DEG C；
(3) composite electrolyte membrane of gained coating protection is dried in vacuo for 24 hours at 60 DEG C, further removes N, N- dimethyl
The composite electrolyte membrane of coating protection can be obtained in formamide.
XRD test is carried out to sulfide prepared by the present embodiment two, XRD is the results show that the principal product of this method preparation is
Li9.54Ge1.74P1.44S11.7I0.3, there are a small amount of by-product Li7PS6, Li7PS6It also being capable of conducting lithium ions.The present embodiment two is made
Standby sulfide carries out SEM characterization, the results show that Li9.54Ge1.74P1.44S11.7I0.3Particle size uniformity, about 100nm.It is right
Composite electrolyte membrane prepared by the present embodiment two carries out SEM characterization and has no bright the results show that composite electrolyte film surface is uniform
Aobvious sulfide bulky grain illustrates that obviously reuniting does not occur in composite membrane-forming process sulfide, and by polymer wrapped, avoids
It is directly contacted with electrode material, improves chemical stability.
Composite electrolyte membrane prepared by the present embodiment two is assembled into symmetrical obstruction battery, obstruction electricity is made with stainless steel gasket
Pole carries out ac impedance measurement, and the ionic conductivity for calculating gained composite electrolyte membrane is 1 × 10-4S/cm。
The composite electrolyte membrane of coating protection prepared by embodiment two is washed into the disk that diameter is 15mm, as electrolyte
Film assembles solid lithium ion battery.Anode is by LiFePO4, Super P, Li9.54Si1.74P1.44S11.7I0.3Quality is pressed with PVDF
Than 80: 10: 5: 5 compositions, cathode is by graphite, SuperP, Li9.54Si1.74P1.44S11.7I0.3With PVDF in mass ratio 80: 10: 5: 5
Composition, battery are assemblied in argon gas glove box and carry out.Constant current charge-discharge loop test, 0.1C electricity are carried out to solid lithium ion battery
Under current density, solid state battery initial capacity is 150.5mAh/g, and capacity retention ratio is 87.3% after circulation 30 weeks.
Embodiment three
Embodiment three provides a kind of composite electrolyte membrane, by Li9.64Si1.74P1.44S11.8Br0.2, polyethylene glycol oxide, poly- carbon
Acid propylene rouge and bis- (trifluoromethane sulfonic acid) imine lithiums composition.Composite electrolyte membrane with a thickness of 180 μm, room temperature heavy ion conductance
Rate is 8 × 10-5S/cm。
Wherein, Li9.64Si1.74P1.44S11.8Br0.2The mass ratio accounted in composite electrolyte membrane is 30%.
The mass ratio that poly- propene carbonate accounts in composite electrolyte membrane is 20%.
The mass ratio that polyethylene glycol oxide accounts in composite electrolyte membrane is 40%.
The mass ratio that lithium hexafluoro phosphate accounts in composite electrolyte membrane is 10%.
Embodiment two also provides a kind of preparation method and application of composite electrolyte membrane, specifically the preparation method is as follows: including
Receive the preparation for preparing the thio lithium fast-ionic conductor step of meter level, composite steps and polyoxyethylene ene coatings, wherein receive and prepare rice
The thio lithium fast-ionic conductor step of grade:
(1) Li is stoichiometrically weighed2S、SiS2、P2S5It is added in N-Methyl pyrrolidone with LiBr, magnetic agitation
For 24 hours, after being uniformly dispersed, solvent is evaporated while stirring, obtains precursor powder；
(2) gained precursor powder calcines 10h at 500 DEG C, obtains nanoscale Li10SnP2S12。
Composite steps:
(1) polyethylene glycol oxide, poly- propene carbonate and N-Methyl pyrrolidone is mixed according to the ratio of mass ratio 2: 1: 50
It closes, the magnetic agitation 2h at 60 DEG C, sufficiently dissolves；
(2) Li is weighed by metering ratio10SnP2S12Above-mentioned solution is added with lithium hexafluoro phosphate, ultrasonic disperse is uniform；
(3) above-mentioned solution is poured into polytetrafluoro molding die, evaporates solvent at 50 DEG C, obtains composite electrolyte membrane.
The preparation of polyoxyethylene ene coatings；
(1) in mass ratio 9: 1 polyethylene glycol oxide and lithium hexafluoro phosphate addition N-Methyl pyrrolidone, magnetic agitation are weighed
2h, dissolution are abundant；
(2) the composite electrolyte film surface for preparing above-mentioned solution coating to step 2, evaporation at constant temperature solvent at 50 DEG C；
(3) composite electrolyte membrane of gained coating protection is dried in vacuo for 24 hours at 70 DEG C, further removes anhydrous acetonitrile,
The composite electrolyte membrane of coating protection can be obtained.
XRD test is carried out to sulfide prepared by the present embodiment three, XRD is the results show that the principal product of this method preparation is
Li10SnP2S12, there are a small amount of by-product Li3PS4, Li3PS4It also being capable of conducting lithium ions.Sulfide prepared by the present embodiment three
SEM characterization is carried out, the results show that Li10SnP2S12Particle size uniformity, about 60~100nm.Three preparation of the present embodiment is answered
Dielectric film progress SEM characterization is closed to have no apparent sulfide bulky grain the results show that composite electrolyte film surface is uniform, say
Obviously reuniting does not occur in bright composite membrane-forming process sulfide, and by polymer wrapped, avoids and directly contact with electrode material,
Improve chemical stability.
Composite electrolyte membrane prepared by the present embodiment three is assembled into symmetrical obstruction battery, obstruction electricity is made with stainless steel gasket
Pole carries out ac impedance measurement, and the ionic conductivity for calculating gained composite electrolyte membrane is 8 × 10-5S/cm。
The composite electrolyte membrane of coating protection prepared by embodiment three is washed into the disk that diameter is 15mm, as electrolyte
Film assembles solid lithium ion battery.Anode is by LiFePO4, Super P, Li10SnP2S12With PVDF in mass ratio 75: 10: 9: 6
Composition, cathode is metal lithium sheet, and battery is assemblied in argon gas glove box and carries out.Constant current charge-discharge is carried out to solid lithium ion battery
Loop test, under 0.1C current density, solid state battery initial capacity is 145.5mAh/g, and capacity retention ratio is after circulation 30 weeks
85.5%.
Composite electrolyte membrane of the invention includes the thio lithium fast-ionic conductor of nanoscale, lithium salts, polyethylene glycol oxide and poly- carbon
Acid propylene rouge.The thio lithium fast-ionic conductor of nanoscale is prepared using solvent method, the thio lithium fast-ionic conductor of nanoscale can uniformly divide
It is dispersed in the blending matrix of polyethylene glycol oxide and poly- propene carbonate, not only provides high ionic conductivity, but also can construct good
Ion transmission channel, and widened electrochemical stability window.It is led in addition, the present invention prepares the fast ion of thio lithium using solvent method
Body, gained particle size are obviously reduced compared with traditional ball-milling method, reach nanoscale, and nano-scale particle can be evenly spread to
In polymer, combined electrolysis further are improved by itself high ionic conductivity and in terms of increasing the amorphous degree of polymer two
The ionic conductivity of matter.
Meanwhile polyethylene glycol oxide is blended with the poly- propene carbonate containing high dielectric constant group, poly- propene carbonate contains
There is highly polar carbonate group, increase the amorphous degree of polyethylene glycol oxide, improves ionic conductivity, while improving polymerization
The mechanical strength and electrochemical window of object film.Meanwhile in polymer after poly- propene carbonate ratio raising, the viscosity of mixed liquor
It reduces, thio lithium fast-ionic conductor dispersion is more uniform.
Furthermore polyoxyethylene ene coatings are coated in composite electrolyte film surface, prevent thio lithium fast-ionic conductor and poly- carbon
Acid propylene rouge is contacted with the graphite cathode of lithium anode or embedding lithium, improves the chemical stability of electrode and electrolyte.
To sum up, it is bad, brilliant both to have improved interfacial contact between electrolyte and electrode for composite electrolyte membrane prepared by the present invention
The big problem of boundary's impedance, and higher ionic conductivity is maintained, while solving chemical phase between electrolyte and negative electrode material
The problem of capacitive difference has broad application prospects in solid state lithium battery field.
Although the present invention is disclosed above by preferred embodiment, however, it is not intended to limit the invention, this any known skill
Skill person can make some changes and embellishment without departing from the spirit and scope of the present invention, therefore protection scope of the present invention is worked as
Subject to claims range claimed.
Claims (10)
1. a kind of composite electrolyte membrane, which is characterized in that including following each component:
The thio lithium fast-ionic conductor of the nanoscale of 10wt.%~60wt.%；
The lithium salts of 10wt.%~40wt.%；
Polyethylene glycol oxide；And
Poly- propene carbonate,
Wherein, the mass ratio of the polyethylene glycol oxide and the poly- propene carbonate is 1: 5~50: 1.
2. composite electrolyte membrane as described in claim 1, which is characterized in that the thio lithium fast-ionic conductor of nanoscale includes
Li4-xSi1-xPxS4-yAyOne or more of, A is F, Cl, Br or I, 0≤y≤0.5 in formula；The thio lithium of nanoscale fastly from
The particle size of sub- conductor is 10nm~100nm.
3. composite electrolyte membrane as described in claim 1, which is characterized in that the lithium salts includes lithium perchlorate, hexafluorophosphoric acid
Lithium, LiBF4, dioxalic acid lithium borate, trifluoromethyl sulfonic acid lithium, bis- (trifluoromethane sulfonic acid) imine lithiums and three (trifluoromethyls
One or more of sulfonic acid) lithium methide.
4. composite electrolyte membrane as described in claim 1, which is characterized in that 100 μm of the thickness of the composite electrolyte membrane~
400 μm, the ionic conductivity of the composite electrolyte membrane is 2 × 10-5S/cm~2 × 10-4S/cm。
5. a kind of preparation method for preparing the composite electrolyte membrane as described in any in Claims 1-4, which is characterized in that institute
The preparation method for stating composite electrolyte membrane includes:
Prepare the thio lithium fast-ionic conductor step of meter level: by Li2S、AS2、P2S5And halogen dispersion is in organic solvent, evaporates solvent
After obtain precursor powder, obtain the thio lithium fast-ionic conductor of nanoscale of halogen doping after calcining, in formula, AS2For SiS2、
GeS2And SnS2In any one；
Composite steps: by polyethylene glycol oxide, poly- propene carbonate and organic solvent Hybrid Heating, the nanoscale of halogen doping is added
Thio lithium fast-ionic conductor and lithium salts, are uniformly dispersed, and pour into molding die, obtain composite electrolyte after evaporation at constant temperature solvent
Film.
6. the preparation method of composite electrolyte membrane as claimed in claim 5, which is characterized in that the organic solvent is anhydrous second
One or more of nitrile, dimethyl sulfoxide, n,N-Dimethylformamide and N-Methyl pyrrolidone.
7. the preparation method of composite electrolyte membrane as claimed in claim 5, which is characterized in that the temperature of the calcining is 300
DEG C~600 DEG C, the heating rate of calcining is 0.1 DEG C/min~10 DEG C/min, and calcination time 4h~2h, the composite steps are 25
DEG C~60 DEG C at carry out.
8. a kind of application of the composite electrolyte membrane as described in any in Claims 1-4, which is characterized in that the compound electric
Plasma membrane is solved in lithium battery.
9. the application of composite electrolyte membrane as claimed in claim 8, which is characterized in that being dissolved in polyethylene glycol oxide and lithium salts has
Solvent is coated on the composite electrolyte membrane, and vacuum constant temperature is dry after solvent evaporation, obtains the protection of polyoxyethylene ene coatings
Composite electrolyte membrane.
10. the application of composite electrolyte membrane as claimed in claim 9, which is characterized in that the thickness of the polyoxyethylene ene coatings
Degree is 5 μm~50 μm, and the temperature of the solvent evaporation is 25 DEG C~60 DEG C, and the dry temperature of the vacuum constant temperature is 40 DEG C~80
DEG C, the dry time 3h~48h of the vacuum constant temperature.
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| CN107394262A (en) * | 2017-07-25 | 2017-11-24 | 深圳市沃特玛电池有限公司 | A kind of preparation method of composite solid electrolyte |
| CN107834104A (en) * | 2017-12-12 | 2018-03-23 | 清陶（昆山）能源发展有限公司 | A kind of composite solid electrolyte and preparation method thereof and the application in solid lithium battery |
| CN108511791A (en) * | 2018-03-08 | 2018-09-07 | 浙江大学 | A kind of quasi-solid electrolyte film and its preparation method and application |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113131005A (en) * | 2021-04-19 | 2021-07-16 | 清华大学深圳国际研究生院 | Polymer electrolyte membrane and preparation method thereof, and metal lithium battery and preparation method thereof |
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